Analytical Chemistry (Qualitative and Quantitative Chemistry)

finals / week 14

TITRIMETRIC METHODS
Titrimetry
 refers to that group of analytical techniques which takes advantage of titers or concentrations of solutions.
 The word "titer" is also used to denote "equivalence" or that amount of a solution required to complete a chemical reaction.
 often refers to the use of some volume of a solution of known concentration to determine the quantity of an analyte.

Types of Titrimetry
Volumetric Titrimetry – establishes a quantity of analyte using volumes of reagents of known concentrations and the knowledge of
the stoichiometry of the reactions between the reagents and the analytes.
Gravimetric Titremetry – determines the quantity of analyte by a measure of the mass of a solution of known concentration.
Coulometric Titremetry – arrives at the amount of analyte by measuring the number of coulombs or total charge required to
complete reaction with the solutions

Concepts and Calculations

Calculation of concentration
- Calculation of molarity
- Preparation of solutions
- dilutions
Calculation of analyte concentration from titration data

Equivalence Point
 is the point where sufficient titrant has been added to be stoichiometrically equivalent to the amount of analyte.

Example: Chloride determination

 50 mL of a 0.1M AgNO3 solution would be required to completely react with 0.005 moles of NaCl!
1 mol   1 mol
AgNO3 (aq) + NaCl (aq)  AgCl (s)↓+ NaNO3 (aq)
0.050 L x 0.1 M 
C x V = 0.050 L x 0.1 M = 0.005 moles

End Point
 is the point at which some detection technique tells you that chemical equivalence has been reached.
 Ideally the end point and the equivalence point should coincide.
  But this rarely happens due to the methods used to detect the end point.
  The difference between the end point and the equivalence point is called a titration error (typically an over-titration).
Primary Standard
 A primary standard is a high purity compound that serves as a reference material in all volumetric and mass titrimetric
methods
 Ideally the titrant solution would be made from a primary standard!
 Titrant solutions must be of known concentration!

Ultrapure/ highly purified copound.

The accuracy of a method is critically dependent on the properties of this compound.

Primary Standard Requirements

1. High Purity
2. Stability in presence of air
3. Absence of any water of hydration which might vary with changing humidity and temperature
4. Dissolve readily to produce stable solutions
5. A relatively large molar mass to minimize
6. Reacts rapidly and stoichiomestrically with analyte

Secondary Standard
 Few materials meet all of the primary standard requirements
 Instead a secondary standard that is standardized with a primary standard!

A secondary is a compound whose purity has been established by chemical analysis and that serves as the reference material for a
titrimetric method analysis.
Less pure compounds- purity must be established by careful analysis

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 Analytical Chemistry (Qualitative and Quantitative Chemistry)
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Standardization
 Is a process in which the concentration of a secondary standard is determined to high level of accuracy by titration with a
primary standard.The conc. of a volumetric sol’n. is determined by titrating it against carefully measured quantity of a primary
or secondary std. or an accurately known vol. of another std. sol’n.

Examples of Primary Standards

 Primary standards for standardization of NaOH
- Potassium acid phthalate (KHP)
 Primary standards for standardization of HCl
- Sodium carbonate

Molar Concentration
 Molarity
 The number of moles of species (x) dissolved in 1 L of solution
 mol/L = M
 M = Number of Moles of Solute (mole) 
Volume of Solution (L)
Weight of Solute(g)
Number of Moles of Solute ( mole )=
g
Normality
MW of solute ( )
mol
 The number of equivalents of solute (x) dissolved in 1 L of solution
 NX = equivalent weight of the solute
Volume of Solution (L)
 N=zM
 where z represents equivalent numbers = the reaction stoichiometric number

Analytical Molarity
 The total number moles of a solute (regardless off it’s chemical state) in one liter of solution
117 (MW of NaCl = 58.5 g/mol)

W NaCl 117.0 g
Mole of NaCl= = =2 .00 moles
MW NaCl 58.9 g /mol
2.00 moles 2.00 mole
M NaCl= = ∨2. 00 M
1.00 L L
o Example:
249 g of H2SO4 dissolved in 1.00 L of water has an analytical concentration of ____ mol/L MW of H2SO4 = 98.0 g/mol
W H 2 S O4
Mole of H 2 S O 4 =
MW H 2 S O 4
294.0 g
¿ =3.00 moles
98 g /mol
Mole H 2 S O 4 3.00 moles
C H 2 S O 4= = =3.00 M
Vol ( L) 1L
 To prepare a solution with 0.500 M of Cl- from BaCl2
o 2H2O. How much of the BaCl2
o 2H2O must be used to prepare 1.00 liter of solution? Assume BaCl2 completely dissociates:
BaCl2 -----> Ba+2 + 2 Cl

1 mole 2 moles
− x1 L
mole BaCL2 mol 2
0.5
L
Analytical Chemistry (Qualitative and Quantitative Chemistry)
finals / week 14

 MW of BaCl2 • 2H2O = 244.2 g/mol

o W of BaCl2 • 2H2O = Mole of BaCl2 (mole) 
    x MW of BaCl2 • 2H2O
= (0.25 moles)(244.2 g/mol)
= 61.1 g
Percent Concentration
 Weight percent (w/w) = mass of solute x 100%
mass of solution
 Volume percent (v/v) = volume of solute x 100%
volume of solution
 weight/volume percent (w/v) = mass of solute (g) x 100%
volume of solution (mL)
Density
- Expresses the mass of a substance per unit volume.
- In SI Units: density unit --- g /mL or kg/L
- Example: Density of water is approximately 1.00 g/mL at 40C.
Specific Gravity
- The ratio of the mass of a substance to the mass of an equal volume of water (at a specified temperature, 200C).
- No-unit or dimensionless
Example
 What is the v/v% of ethanol in a solution prepared by mixing 5.00 mLof ethanol with enough water to give 1.00 L of
solution?
Solute: ethanol
1) Volume of solute (ethanol) = 5.00 mL = 5.00 x10-3 L
2) Volume of solution = 1.00 L
3) Volume percent (v/v) = volume of solute x100%
volume of solution

= 5.00 x10-3 L x 100% 

1.00
= 0.500%
VOLUMETRIC CALCULATIONS
Titration Data
 Problem: The molarity of the NaOH titrant is known and we want to find the molarity of the HCl solution.
- We know: molarity of NaOH, volume of HCl.
- What do we want? Molarity of HCl.
- What do we do? Take a known volume of the HCl solution, measure the volume of NaOH required to react completely with
the HCl.
Volumetric Calculations
 NaOH + HCl  NaCl + H2O
Mole NaOH = Mole HCl
CNaOH x VNaOH = CHCl x VHCl
Mole NaOH = C NaOH x V NaOH 
Mole HCl C HCl x V HCl
 The titration of 50.00 mL of an unknown concentration of H2SO4 with standardized base required 25.00 mL of 0.1000 M NaOH.
What is the unknown concentration of H2SO4 ?

The stoichiometry is:

2 NaOH (aq) + H2SO4 (aq) ----> 2 H2O + Na2SO4 (aq)
2 moles 1 mole

 Given: V H2SO4 = 50 mL = 0.50 L

C NaOH = 0.1000 M

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Analytical Chemistry (Qualitative and Quantitative Chemistry)
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V NaOH = 25 mL = 0.25 L
C H2SO4 = ?
C H2SO4 x V H2SO4 = mole H2S04
C NaOH x V NaOH      mole NaOH

C H2SO4 = mole H2SO4 x C NaOH x V NaOH

V H2SO4 x mole NaOH 

C H2SO4 = 1 x 0.1000M x 0.50 L

2 x 0.25 L
= 0.025 M 
Weight Titrations
 In this technique, the volume of titrant delivered is weighed and the moles delivered calculated from the "weight molarity“
 C weight = Number of moles of Solute (mole)
Weight of Solution (kg)

Advantages of Weight Titration

- Calibration of glassware and pipette
- Temperature independence
- Greater precision and accuracy (readily measure at +0.1 mg)
- More easily automated than volumetric titration
Disadvantages of Weight Titration
- Relatively elaborate (expensive) equipment
- Tedious
- Time – consuming (sometimes)